(i) Field of the Invention
This invention relates to naturally-occurring thiophenes, acetylenes and synthetic, structurally-related derivatives, analogues or acetylenic compounds, to compositions containing such compounds, and to the use of such compositions as insect control agents with a novel phototoxic mode of action.
(ii) Description of the Prior Art
It is now well known that many hydrocarbon compounds containing non-heterocyclic groups therein have pesticidal activity and can provide pesticidal compositions. Among the patents which disclose such compounds, and that use, are the following Canadian Patents: 508,018, 675,157, 720,767, 734,397, 843,918, 869,518 and 1,028,945. However, many of such pesticides are neurotoxins, with the result that many insects develop resistance thereto.
The novel phototoxic mechanism of thiophenes and related acetylenes is a means of overcoming this resistance problem. Phototoxicity involves the absorbtion of light by the sensitizer molecule (thiophene or acetylene) and subsequent reaction of the sensitizer in its excited state causing deleterious biological effects. Discovery of the phototoxic effects of thiophenes to nematodes were first reported by F. Gommers (1972, Nematalogica 18, 458) and discovery of the phototoxic effects of polyacetylenes to microorganisms by Towers et al. (1977, Lloydia 40, 487-496).
Early work reports the toxicity of acetylenes and thiophenes to invertebrates without mention of the role of light in the process. For example, U.S. Pat. No. 3,050,442 issued Aug. 21, 1962 to J. D. Bijloo et al, provided a teaching that compositions containing ##STR1## wherein n represents a number selected from the group consisting of 0 and 1, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents substituents selected from the group consisting of hydrogen, methyl propionyl, halogen, nitro, acetyl and phenyl radicals, with the further proviso that when n represents 0, then, R.sub.3 represents, in addition, the thiophene radical and R.sub.2 and R.sub.4 represent only hydrogen. Within such constraints, i.e. when n=1 and R.sub.1 =R.sub.2 =R.sub.3 =R.sub.4 =H, the formula represents the naturally-occurring compound ##STR2## (.alpha.-terthienyl). The patentee taught that such a compound would have pesticidal effects and could be used for combatting insect pests.
It has been reported that some naturally-occurring polyacetylenes and their thiophene derivatives are toxic to invertebrates. Thus, it has been reported that cis-dehydromatricaria ester isolated from Solidago altimissa, and tridec-1-ene-3,5,7,9,11-pentyne isolated from Xanthium canadense (see S. Nakajima et al, 1977, Agric. Biol. Chem., 41, 1801-1805) both of which are widely distributed in the Asteraceae, are ovicidal to the fruit fly Drosophila melanogaster and the house fly, Musca domestica. Several polyacetylenes, e.g., .alpha.-terthienyl from Tagetes spp (see A. R. Verhagen et al, 1974 Arch. Dermatol, 110, 441) and two isomeric polyacetylenes from Carthamus tinctorium (see S. Kogiso et al, 1976 Agric. Biol. Chem. 40, 2085-2089) have been found to be nematocidal.
It has also been taught (see D. McLachlan et al, 1982, Experimentia, 38, 1061-1062) that 1-phenylhepta-1,3,5-triyne (PHT), a polyacetylenic compound isolated from Bidens pilosa L. (Asteraceae) has antifeedant properties towards larvae of the polyphagous insect Eaxoa messoria.
Recent work has demonstrated that the toxicity of polyacetylenes and thiophenes to insects is greatly enhanced by sources of radiation in the range 300-400 nm. Nine of 14 substances tested were phototoxic to mosquito larvae of Aedes aegyptii at 500 ppb (C. K. Wat et al, 1981, Biochem. Syst. & Ecol. 9, 59-63), yet had no effect at this concentration in the dark. The exceptional phototoxicity of two compounds, .alpha.-terthienyl and 2-(non-trans en-3',5',7'-triynyl) furan were subsequently reported (J. T. Arnason et al, 1981, Biochem. Syst. & Ecol. 9, 63-69). Analogues and derivatives of these compounds were also found to be toxic to mosquito larvae (J. T. Arnason et al, 1986, Phytochem., in press and J. Kagan et al. 1983 Insect Sci. App. 4, 377-381). Large scale synthesis of .alpha.-terthienyl permitted field trials in natural breeding pools of mosquito larvae that have demonstrated that good control can be achieved at applications of 100 g active ingredient/ha. with acceptable non target effects. (Philogene et al. 1985, J. Econ. Ent. 78, 121 and 1986, J. Chem. Ecol. in press).
With insects other than mosquito larvae, there are reports of the phototoxicity of .alpha.-terthienyl to larvae of Manduca sexta (K. Downum et al, 1984, Pest. Biochem. Physiol. 22, 104) and to larvae of Euxoa messoria (D. Champagne et al, 1984 Experientia, 40, 577. J. Kagan et al, 1983, Experimentia, 39, 402-403) reported photoovicidal activity several substances to Drosophila melanaogaster.
D. E. Champagne et al. in Journal of Chemical Ecology Vol. 12 No. 4, 1986 p 835, discloses the effect of the following seven structures on three species of herbivorous insects: a monothiophene, a bithiophene, .alpha.-terthienyl, phenylheptatriyne, phenylheptadiynene, phenylheptadiynene acetate and matricaria lactone. It was taught that the biosynthetically derived thiophenes were more toxic than their acetylene precursors and that toxicity increased with increasing number of thiophene rings for this series. ##STR3##
Towers et al, in Canadian Patent No. 1,173,743 patented Sept. 4, 1984, provided a method for protecting plants from herbivores and pathogens, by applying, to the plants, a composition comprising an inert carrier and a biocidal-amount of a conjugated polyacetylene; and subjecting the composition, when on those plants, to UV radiation in the range of 300 nm to 400 nm. That patent also provided a pesticidal composition comprising an inert carrier and an amount of a conjugated polyacetylene which, when applied at a rate of 0.1 lb/acre to a plant, and then subjected to UV radiation in the range of 300 nm to 400 nm, had pesticidal activity. The conjugated polyacetylenes taught therein could be one or more of the following:
1-phenylhepta-1,3,5-triyne, PA0 [5-(but-3-en-1-ynyl)]5'-methyl.alpha.-bithiaine PA0 methyl-4-methythiodeca-2,4-dien-6,8-diyn-1-oate, PA0 methyldodeca-cis.-2,8,10-trien-4,6-diyn-1-oate, PA0 (2.sup.1 -phenylethyl)-undeca-2,4-dien-8,10-diyn-1-carboxamide, PA0 dodec-1-en-3,5,7,9,11-pentayne, PA0 2-(but-3'-yn-2'-onylidenyl)-5-pentyl-tetrahydropyran, PA0 3-[prop-1-yne]-6-(hexa-3'3'-dien-1-ynyl)-1,2-dithianine, PA0 2-(3'-buten-1-ynyl)-5-(3'-penten-1-ynyl)-thiophene, PA0 .gamma.-(2'-neuynylidenyl)-.gamma.-but-2-enyrolactone, PA0 1-acetoxytetradeca-4,6,12-trien-8,10-diyne, PA0 tetradeca-4,6-dien-8,10,12-triynyl-sec-butenoate, PA0 1,2-dihydroxytrideca-3,5-dien-7,9,11-triyne, PA0 2-(non-trans-1'-en-3',5',7'-triynyl)-tetrahydropyran, PA0 2-(non-trans-en-3',5'7'-triynyl)-furan, PA0 heptadeca-1,9,6-trien-4,6-dien-3-one, PA0 1,3-dihydroxytetradeca-4,6,12-trien-8,10-diyne, PA0 1-hydroxy-7-phenylhepta-2-en-4,6-diyne, PA0 2-chloro-1-hydroxytrideca-3,11-dien-5,7,9-triyne, PA0 7-phenylhepta-2-en-4,6-diynal, PA0 .gamma.-(hex-4'-en-2'-ynylidenyl)-.gamma.-but-2-enyrolactone, PA0 heptadeca-1,8,15-trien-11,13-diyne, PA0 nonadeca-1,7,9,17-tetraen-11,13-diyne, PA0 3,4-dihydroxytrideca-1,5,11-trien-7,9-diyne, PA0 trideca-1,3,5,11-tetraen-7,9-diyne, PA0 1,2-dihydroxytrideca-3,11-dien-5,7,9-triyne, PA0 1-hydroxytetradeca-6,8,11,13-tetraen-10-yne, PA0 1-acetoxytetradeca-6,8,12,14-tetraen-10-yne, PA0 1,3-dihydroxytetradeca-trans, trans-4,6-dien-8,10,12-triyne, PA0 1,3-diacetoxytetradeca-4,6-dien-8,10,12-triyne, PA0 tetradeca-1,8,13-trien-4,6-diyn-3-one, PA0 1-hydroxy-7-phenylhepta-2,4,6-triyne, PA0 7-phenylhepta-2,4,6-triynal; PA0 5-acetoxy-7-(penta-2',4'-diynylidenyl)-2,6-dioxa-(4,4-spiro-nona-3,8-diene) ; PA0 1-[5'-pentyl-3',4',5',6'-tetrahydrophyranilidenyl]but-3-yne-2-one; and PA0 (3-hydroxy-2-[trans-1'-nonen-3,5,7-trynyl]-tetrahydropyran. PA0 #1=K. Tamao et. al., Tetrahedron, Vol. 38 #22, 3347-3354, (1982). PA0 #2=References given in B. J. R. Philogene, et. al., Journal of Economic Entomology, Vol 78 #1 pp 121-126, (1985). PA0 #3=J. W. Sease and L. Zechmeister, J. Am. Chem. Soc 69, 270, (1947). PA0 #4=A. Meuller et. al., Acta Chem Acad Sci Hung, 52, 261 (1961) Chem Abstr, 67, 64222 (1967). PA0 #5a=J. H. Uhlenbroek and J. D. Bijloo, Rec Trav Chim, 79, 1181-96, (1960) Eng. PA0 #5b=H. J. Bestmann and W. Schaper, Tetrahed. Letters, No 3, pp 243-244 (1979). PA0 #6=J. Kagan, et. al., J. Org. Chem., 48, 4076-4078, (1983). PA0 #7=H. Wynberg et. al., J. Am. Chem. Soc. 79, 1972 (1957). PA0 #8=F. Bohlmann et. al., Chem. Ber. 99, (3), 984, (1966). PA0 #9=H. Wynberg et. al., J. Am. Chem. Soc., 82, 1447, (1960). PA0 #10=K. E. Schulte et. al., Arch. Pharm. 296, 456, (1963). PA0 #11=M. Sy et. al., J. Chem. Soc., 1975, (1954). PA0 #12=CA 55: P 1800 2d. PA0 #13=CA 58: P4991a. PA0 #14=H. Wynberg et. al., J. Am. Chem. Soc., 89, #14, 3487-94. (1967). PA0 #15=A. Carpita, R. Rossi, and C. Veracini, Tetrahedron Vol. 41, #1, pp 1919-1929, (1985). PA0 #16=P. Riberreau, G. Quequiner and P. Pastour, Bull. Soc. Chim. Fr., 4, pp 1581-7, (1972). PA0 #17=J. Meier, W. Chodkiewicz, P. Cadiot, and A. Willemart, Compt. Rend. 245, 1634, (1957). PA0 #18=Patented by T. Arnason et al., Canadian Patent No. 1,169,767, and Canadian Patent No. 1,173,743. PA0 #19=Commercially Available PA0 #20=P. Chauvin, J. Morel, P., Pastour and J. Martinez. Bull. Soc. Chim. Fr. (9-10 Pt 2) pp 2079-85, (1974). PA0 #21=P. Raymond, Compt. Rend. 202, pp 854-6, (1936) PA0 #22=E. Campaigne, and L. Fedor, Journal of Heterocyclic Chem. 1 (5), pp 242-4, (1964). PA0 #23=R. E. Atkinson, R. F. Curtis and J. A. Taylor, J. Chem. Soc (C) 7, pp 578-82, (1967). PA0 #24=R. E. Atkinson, R. F. Curtis And G. J. Philips, Chem. Ind, 51, pp 2101-2102, (1964). PA0 #25=CA 96: P117583r; CA 96 P16085z. PA0 #26=F. Bohlmann et al, Tett. Lett, (19) pp 1385-8, (1965).
Other compounds which are structurally related to the above discussed compounds which have been disclosed in the scientific literature are these listed in the following Table 1.
TABLE 1 __________________________________________________________________________ COMPOUND DISCLOSED IN (FORMULA) COMPOUND NO. REFERENCE __________________________________________________________________________ NO. The following fourteen compounds of Formula I: FORMULA I ##STR4## 1. R.sup.1 = R.sup.2 = Br 2. R.sup.1 = R.sup.2 = CH.sub.3 3. R.sup.1 = R.sup.2 = CO.sub.2 H 4. R.sup.1 = R.sup.2 = CO.sub.2 CH.sub.3 5. R.sup.1 = R.sup.2 = C(CH.sub.3).sub.3 #2, #3 and #5 #3, #12, #13 #6 #6 #11 6. R.sup.1 = CH.sub.3 ; R.sup.2 #3H 7. R.sup.1 = CO.sub.2 H; R.sup.2 #6H 8. R.sup.1 = CO.sub.2 CH.sub.3 ; R.sup.2 = #6 9. R.sup.1 = tritium; R.sup.2 #8COCH.sub.3 10. R.sup.1 = R.sup.2 = COCH.sub.3 #8, #9 11. R.sup.1 = R.sup.2 = C.sub.6 H.sub.5 #10 12. R.sup.1 = CH.sub.2 OH; R.sup.2 #11 13. R.sup.1 = Br; R.sup.2 = H #12 and #13 14. R.sup.1 = CHO; R.sup.2 = H #6 FORMULA II ##STR5## 15. #1 and #4 FORMULA III ##STR6## 16. R.sup.1 = R.sup.2 = R.sup.3 = R.sup.4 = R.sup.5 = R.sup.6 = CH.sub.3 ; R.sup.7 = H 17. R.sup.1 = R.sup.2 = R.sup.5 = R.sup.6 = R.sup.7 = H; R.sup.3 = R.sup.4 = CH.sub.3 18. R.sup.1 = R.sup.2 = R.sup.5 = R.sup.6 = R.sup.7 = CH.sub.3 ; R.sup.3 = R.sup.4 = H 19. R.sup.1 = R.sup.4 = R.sup.6 = R.sup.7 = H; R.sup.2 = R.sup.3 = R.sup.5 = CH.sub.3 #5 #5a and 5b #5 #5 FORMULA IV ##STR7## 20. #5 and #7 FORMULA V ##STR8## 21. R.sup.1 = R.sup.2 = R.sup.3 = R.sup.4 = tritium #8 FORMULA VI ##STR9## 22. #5a FORMULA VII ##STR10## 23. #14 FORMULA VIII ##STR11## 24. #7 The following two compounds of Formula IX: FORMULA IX ##STR12## 25. R.sup.1 = H; R.sup.2 = Br 26. R.sup.1 = R.sup.2 = Br 15 #15 FORMULA X ##STR13## 27. #16 FORMULA XI ##STR14## 28. #17 and #18 FORMULA XII ##STR15## 29. #19 FORMULA XIV ##STR16## 30. #20 FORMULA XV ##STR17## 31. #24 and #25 FORMULA XVI ##STR18## 32. #21, #22 and #23 FORMULA XVII ##STR19## 33. #18 FORMULA XVIII ##STR20## 34. #26 __________________________________________________________________________
In the above table, the references identified as numbers 1-28 are as follows:
Nevertheless, it is well established that the biological activity of naturally-occurring thiophenes and acetylenes and synthetic, structurally-related derivatives, analogues or acetylenic compounds is not predictable. Moreover, such naturally-occurring thiophenes, acetylenes and synthetic, structurally-related derivatives, analogues or acetylenic compounds, to be biologically useful, should also be relatively stable but should leave no toxic residue, and such characteristics are also not predictable. Accordingly, it is an object of this invention to provide novel phototoxic, naturally-occurring thiophenes, acetylenes, or synthetic, structurally-related derivatives, analogues or acetylenic compounds which have a selected balance between stability and biodegradability and consequently have improved utility as insect control agents.
It would also be desirable, and it is also an object of this invention, to provide pesticidal compositions containing phototoxic, naturally-occurring thiophenes, acetylenes, or synthetic, structurally-related derivatives, analogues or acetylenic compounds, in which such phototoxic, naturally-occurring thiophenes, acetylenes or synthetic, structurally-related derivatives, analogues or acetylenic compounds are relatively stable but which are eventually biodegradable and would therefore leave no long-lived toxic residues.
It would also be desirable, and it is therefore yet another object of this invention to provide methods for insect control involving the use of phototoxic, naturally-occurring thiophenes, acetylenes, or synthetic, structurally-related derivatives, analogues or acetylenic compounds which are relatively stable but which are eventually biodegradable and generally would leave no long-lived toxic residues.
(ii) Statements of Invention
This invention now provides a method for controlling insects which are harmful to agriculture, and forestry and are harmful with respect to veterinary and human medicine, which method comprises: (a) applying to a locus infested with such insects, a composition comprising a carrier and a biocidal-amount of a phototoxic naturally-occurring thiophene, acetylene or synthetic, structurally-related derivatives, analogues or acetylenic compounds selected from the group consisting of the following numbered compounds identified as numbers 1 through 70:
(a) the fourteen compounds, 1-14, of Formula I: ##STR21##
(b) the compound, 15, of Formula II: ##STR22##
(c) the four compounds, 16-19, of Formula III: ##STR23##
(d) the compound, 20, of Formula IV: ##STR24##
(e) the compound, 21, of Formula V: ##STR25##
(f) the compound, 22 of Formula VI: ##STR26##
(g) the compound, 23, of Formula VII: ##STR27##
(h) the compound, 24, of Formula VIII: ##STR28##
(i) the two compounds, 25 and 26, of Formula IX: ##STR29##
(j) the compound, 27, of Formula X: ##STR30##
(k) the compound, 28, of Formula XI: ##STR31##
(l) the compound, 29, of Formula XII: ##STR32##
(m) the compound, 30, of Formula XIV: ##STR33##
(n) the compound, 31, of Formula XV: ##STR34##
(o) the compound, 32, of Formula XVI: ##STR35##
(p) the compound, 33, of Formula XVII: ##STR36##
(q) the compound, 34, of Formula XVIII: ##STR37##
(r) a novel derivative, 35-47 of the Formula XIX: ##STR38##
(s) a novel derivative, 48, of the Formula XX: ##STR39##
(t) a novel analogue or a novel acetylene compound, 49-52 of the following Formulae, namely: ##STR40## and
(u) a novel derivative 53-70 of .alpha.-terthienyl of Formula XXV (where a dot indicates the point of attachment): ##STR41## and
(b) subjecting that composition at that locus to UV radiation in the range of about 300 nm to about 400 nm for a sufficient time to impart, to such phototoxic naturally-occurring thiophene, acetylene or synthetic, structurally-related derivative, analogue or acetylenic compound such insect controlling activity.
This invention also provides an insect control composition comprising a carrier and a biocidally-effective amount of a phototoxic, naturally-occurring thiophene, acetylene, or synthetic, structurally-related derivative, analogue or acetylenic compound selected from the group consisting of the following compounds identified as numbers 1 through 70:
(a) the fourteen compounds, 1-14, of Formula I: ##STR42##
(b) the compound, 15, of Formula II: ##STR43##
(c) the four compounds, 16-19, of Formula III: ##STR44##
(d) the compound, 20, of Formula IV: ##STR45##
(e) the compound, 21, of Formula V: ##STR46##
(f) the compound, 22 of Formula VI: ##STR47##
(g) the compound, 23, of Formula VII: ##STR48##
(h) the compound, 24, of Formula VIII: ##STR49##
(i) the two compounds, 25 and 26, of Formula IX: ##STR50##
(j) the compound, 27, of Formula X: ##STR51##
(k) the compound, 28, of Formula XI: ##STR52##
(l) the compound, 29, of Formula XII: ##STR53##
(m) the compound, 30, of Formula XIV: ##STR54##
(n) the compound, 31, of Formula XV: ##STR55##
(o) the compound, 32, of Formula XVI: ##STR56##
(p) the compound, 33, of Formula XVII: ##STR57##
(q) the compound, 34, of Formula XVIII: ##STR58##
(r) a novel derivative, 35-47, of the Formula XIX: ##STR59##
(s) a novel derivative, 48, of the Formula XX: ##STR60##
(t) a novel analogue or a novel acetylene compound, 49-52 of the following Formulae, namely: ##STR61## and
(u) a novel derivative 53-70 of .alpha.-terthienyl of Formula XXV (where a dot indicates the point of attachment): ##STR62##
This invention also provides an insect control composition comprising a carrier and a biocidally-effective amount of a phototoxic, naturally-occurring thiophene, acetylene, or synthetic, structurally-related derivative, analogue or acetylenic compound selected from the group consisting of the following compounds identified as numbers 35 through 70: ##STR63##
(s) a novel derivative, 48, of the Formula XX: ##STR64##
(t) a novel analogue or a novel acetylene compound, 49-52 of the following Formulae, namely, ##STR65## and
(u) a novel derivative 53-70 of .alpha.-terthienyl of Formula XXV (where a dot indicates the point of attachment): ##STR66##
(iii) Other Features of This Invention
In one feature of this method embodiment of this invention, the selected phototoxic, naturally-occurring thiophene, acetylene, or synthetic, structurally-related derivative, analogue or acetylenic compound is a compound selected from those identified above as numbers 1 through 34.
In accordance with another feature of this method embodiment of the present invention, the selected phototoxic, naturally-occurring thiophene, acetylene or synthetic, structurally-related derivative, analogue or acetylenic compound is a novel derivative which is selected from those identified above as numbers 35 through 48.
In accordance with yet another feature of this method embodiment of the invention, the selected phototoxic, naturally-occurring thiophene, acetylene or synthetic, structurally-related derivative, analogue or acetylenic compound is a novel analogue or acetylenic compound which is selected from those identified above as numbers 49 through 52.
In accordance with still another feature of this method embodiment of the invention, the selected phototoxic, naturally-occurring thiophene, acetylene or synthetic, structurally-related derivative, analogue or acetylenic compound is a novel analogue or acetylenic compound which is selected from those identified above as numbers 53 through 70.
In accordance with one feature of this composition embodiment of the present invention, the selected phototoxic, naturally-occurring thiophene, acetylene, or synthetic, structurally-related derivative, analogue or acetylenic compound is selected from those identified above as numbers 1 through 34.
In accordance with another embodiment of this composition embodiment of the present invention, the selected phototoxic, naturally-occurring thiophene, acetylene, or synthetic, structurally-related derivative, analogue or acetylenic compound is a novel derivative selected from those identified above as numbers 35 through 48.
In accordance with yet another embodiment of this composition embodiment of this invention, the selected phototoxic, naturally-occurring thiophene, acetylene, or synthetic structurally-related derivative, analogue or acetylenic compound is a novel analogue or acetylenic compound selected from those identified above as numbers 49 through 52.
In accordance with still another embodiment of this composition embodiment of this invention, the selected phototoxic, naturally-occurring thiophene, acetylene, or synthetic structurally-related derivative, analogue or acetylenic compound is a novel analogue or acetylenic compound selected from those identified above as numbers 53 through 70. Invention are primarily suitable for the selective control of many insects, including mosquitoes and blackflies.
The compositions of embodiments of this invention may furthermore be used by themselves or in conjunction with other well-known biodegradable pesticides. The compositions of embodiments of this invention may also include a synergistic carrier or an inert carrier. In addition, the composition may include at least one of the following additives; namely, solvents, diluents, dispersing agents and wetting agents. The compositions of embodiments of this invention may advantageously be used in the form of powders, strewable preparations, granules, solutions, emulsions and suspensions. As will be evident hereafter, these are provided by the addition of liquid and/or solid vehicles or diluents and, if desired, of surface active agents, for example, wetting, adherent, emulsifying and/or dispersing agents.
The compositions of embodiments of this invention may be provided in the form of solutions for immediate spraying using suitable organic solvents, for example, low molecular weight alcohols, hydrocarbons, e.g., alkylated naphthalene or tetrahydronaphthalene if desired with the use of xylene mixtures, cyclohexanols, ketones or chlorinated hydrocarbons, e.g., tetrachlorethane, trichloroethylene or trichlorobenzenes or tetrachlorobenzenes. Other suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions.
The compositions of embodiments of this invention may alternatively be provided in the form of aqueous mixtures using emulsion concentrates, pastes or wettable array powders and adding water thereto. Suitable emulsifying or dispersing agents are non-ionic products, for example, condensation products of ethylene oxide with aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon radical with 10 to 30 carbon atoms with ethylene oxide, e.g., the condensation product from octadecyl alcohol with 25 to 30 mols of ethylene oxide, or soya bean fatty acid with 30 mols of ethylene oxide, or commercial oleylamine with 15 mols of ethylene oxide, or dodecylmercaptan with 12 mols of ethylene oxide.
Suitable anionic emulsifying agents include the sodium salt of dodecyl alcohol sulfuric acid ester, the sodium salt of dodecyl benzenesulfonic acid, the potassium or triethanolamine salt of oleic or abietic acid, of mixtures of these acids, and, the sodium salt of a petroleum-sulfonic acid.
Suitable cationic dispersing agents include quaternary ammonium compounds, e.g. cetyl pyridinium bromide or dihydroxyethyl benzyldodecyl ammonium chloride.
The compositions of embodiments of this invention may further be prepared in the form of dusting and scattering preparations using solid vehicles including talcum, kaolin, bentonite, calcium carbonate or phosphate, coal, cork meal, wood meal or other materials of vegetable origin. It is very advantageous to manufacture the preparations in the form of granulates. With the different forms in which the preparations are used, conventional additives that improve the distribution, adhesion, stability towards rain or penetration, e.g. fatty acids, resins, glue, casein or alginates may also be used. Other suitable carriers include, for example, mineral earths, for example, tonsil, silica gel, talc, kaolin, attaclay, limestone and silica acid, and vegetable products, for example, meals.
The compositions of embodiments of this invention may also be admixed with a wetting agent, with or without an inert diluent, to form a wettable powder which is soluble or dispersible in water, or may be mixed with the inert diluent to form a solid or powdery product. Inert diluents with which the active ingredient may be incorporated include solid inert media comprising powdered or divided solid materials, for example, clays, sands, talc, mica, peat, fertilizers and the like, such products either comprising dust or larger particle size materials, e.g., granules.
The wetting agents used may comprise anionic compounds, e.g., soaps, fatty sulphate esters, e.g., dodecyl sodium sulphate, octadecyl sodium sulfate and cetyl sodium sulphate, fatty aromatic sulphonates, e.g., alkyl benzene sulphonates or butyl naphthalene sulphonate, more complex fatty sulphonates, e.g., the amide condensation product of oleic acid and N-methyl taurine or the sodium sulphonate of dioctyl succinate.
The wetting agents may also comprise non-ionic wetting agents, e.g., condensation products of fatty acids, fatty alcohols or fatty substituted phenols with ethylene oxide, or fatty esters and ethers of sugars or polyhydric alcohols, or the products obtained from the latter by condensation with ethylene oxide, or the products known as block copolymers of ethylene oxide and propylene oxide. The wetting agents may also comprise cationic agents, e.g., octyl trimethyl ammonim bromide and the like. Other suitable surface-active agents include, for example, calcium lignin sulphonate, polyoxyethylenealkyl phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof.
The phototoxic naturally-occurring thiophenes, acetylenes or synthetic, structurally-related derivatives, analogues or acetylenic compounds may be provided in the form of a microincapsulated agent, in a manner well known to those skilled in the art. In this way the stability of the naturally-occurring thiophenes, acetylenes or synthetic, structurally-related derivatives, analogues or acetylenic compounds prior to use may be extended.
Suitable formulations, in the forms of stable emulsions are as follows:
______________________________________ PREFERRED COMPONENT AMOUNT USEFUL AMOUNT ______________________________________ .alpha.-Terthienyl about 5% by weight about 2-10% by weight ATLOX 3403F about 4.1% about 2-10% by weight by weight ATLOX 3403F about 3.4% about 2-10% by weight by weight Suitable Solvent about 87.5% balance by weight of xylene ______________________________________ (ATLOX is the trade mark of Atkemix Inc., Brantford, Ontario, Canada, for a series of emulsifers developed for use with agricultural products)
Suitable formulations in the forms, of synergistic compositions are as follows:
______________________________________ PREFERRED COMPONENT AMOUNT USEFUL AMOUNT ______________________________________ .alpha.-Terthienyl about 5% by weight about 2-10% by weight piperonyl about 5% by weight about 2-10% by weight butoxide ATLOX 3403F about 4.1% about 2-10% by weight by weight ATLOX 3404F about 3.4% about 2-10% by weight by weight Suitable Solvent about 82.5% balance by weight of xylene ______________________________________
In the use of the compositions of embodiments of this invention as insect control agents, the rate of application may comprise, for example, about 0.01-2 lbs/acre, e.g., about 1.5 lbs/acre.
The total proportion of the phototoxic, naturally-occurring thiophenes, acetylenes, or synthetic, structurally-related derivatives, analogues or acetylenic compounds in the various compositions of embodiments of this invention may vary within wide limits. For example, the compositions may contain approximately 10-80% by weight of phototoxic, naturally-occurring thiophenes, acetylenes or synthetic, structurally-related derivatives, analogues or acetylenic compounds, approximately 90-20% by weight of liquid or solid carrier, and also, if desired, up to about 20% by weight of the carrier of one or more surface-active agents. The rate of dilution of the phototoxic, naturally-occurring thiophenes, acetylenes or synthetic, structurally-related derivatives, analogues or acetylenic compounds in an aqueous spray is not critical and may, for example, be about 1-10 kg/ha phototoxic, naturally-occurring thiophenes, acetylenes or synthetic, structurally-related derivatives, analogues or acetylenic compounds in 300 liters/ha water and about 0.1% surface-active agent, e.g., those mentioned above as wetting agents.
The compositions of embodiments of this invention may be applied in the usual manner, for example, with water as carrier lb/acre. It is also possible to apply the active compounds by the so-called "low volume" and "ultra-low volume" methods and it is also possible to apply them in the form of so-called microgranules.